JPH036272A - Pigment preparation - Google Patents

Abstract

PURPOSE: To obtain a pigment preparation for coloring leather obtained by mixing a pigment and a liquid oligourethane in a predetermined wt. ratio and further compounding an additive with the resulting mixture if necessary and excellent in light fastness and not deteriorating the bending strength and low temp. resistance of leather.

CONSTITUTION: Inorg. pigment (e.g; titanium dioxide) and (or) org. pigment (e.g; an anthraquinone pigment) (A), a liquid oligourethane (B) and a necessary additive (e.g; solvent, thickener) (C) are mixed so that a wt. ratio of component A/component B becomes 1/0.1-50 to prepare a pigment preparation suitable for coloring a finish agent of leather and leather cloth. As the liquid oligourethane, oligourethane with a mol.wt. of 5,000-50,000 containing a sterically hindered free isocyanate group or a protected isocyanate group is pref. used.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigment preparations and their use for the coloring of leather and leather fabric dressing agents.

The coloring of water-insoluble finishes for leather and leather fabrics based on polyurethanes or water-insoluble cellulose esters using pigment preparations is known.

Pigment preparations used for this purpose are mainly based on collodion, cellulose acetate, cellulose acetobutyrate, ethyl cellulose or polyvinyl chloride-polyvinyl acetate copolymers, in addition to the pigment and the usual additives such as solvents. A pigment binder is included with or without the addition of a plasticizer such as dibutyl phthalate. These pigment preparations are
The properties of the finishes on leather and leather imitations and the properties of their final products are often adversely affected. On the one hand, it stiffens the leather or leather imitation, reduces its wet and dry bending strength, and reduces its low temperature resistance.

On the other hand, it exudes. In particular, light fastness and yellowing or adhesion under the influence of heat are adversely affected by known composition components.

Attempts to overcome these drawbacks have been made by using polyurethanes identical or similar to those used as binders in leather finishing compositions or as binders in leather fabric coatings as pigment binders. In this way, the mentioned disadvantages are somewhat alleviated. However, since, for example, polyurethanes are only compatible to a very limited extent with each other and with collodion and other cellulose derivatives, it is necessary to use precisely balanced pigment preparations for each finish composition.

A need has thus arisen for a pigment preparation which is universally suitable for use in any leather and leather fabric finishing and which, furthermore, does not have the disadvantages of the known pigment preparations. Preparations with binders introduced by polymerization or admixture into the finishing or coating composition are particularly suitable.

The invention comprises A) an inorganic and/or organic pigment, B) a liquid oligourethane, and, if appropriate, C) one or more additives conventional in pigment preparations, with the exception that A)
:B) in a weight ratio of 120°1 to 50.

The pigment is preferably dispersed in the oligourethane.

Suitable preparations include: A) 2 to 60% by weight of organic pigments, particularly preferably 5 to 30% by weight, or 2 to 80% by weight of inorganic pigments;
, particularly preferably from 10 to 65% by weight, B) from 5 to 98% by weight of an oligourethane, and C) from 5 to 90% by weight, particularly preferably from 8 to 30% by weight of an additive, especially a solvent, with the exception that A)+B )+C) totaling 100% by weight.

Suitable oligourethanes have sterically hindered or protected isocyanate groups. Very particular preference is given to oligourethanes which can react with other polymers present under the conditions of application.

If appropriate, the pigment preparations may contain customary additives such as solvents, fillers or thickeners.

Suitable solvents are alcohols such as isobutanol, cyclohexanol, tert-butanol, diacetone alcohol, ethyl glycol, glycol monomethyl ether, ketones such as methyl ethyl ketone, cyclohexanone, esters such as butyl acetate, heptathalic acid esters such as dimethyl phthalate, dibutyl phthalate. , dioctyl phthalate, phosphoric acid esters such as tricresyl phosphate, adipate esters such as dibutyl adipate, alkylsulfonate esters such as phenyl or tolyl pentadecane sulfonate, i.e. products generally known for the plasticization of nitrocellulose or PVC, or methoxyglobil or ethoxypropyl acetate, or acid amides such as dimethylformamide or methylpyrrolidone, and some hydrocarbons such as benzene, toluene or xylene. Cyclohexanone, dimethylformamide or methoxypropyl acetate are preferred.

Solvents with a boiling point above 120°C are particularly suitable.

Solvents that do not contain OH or NH groups are preferably used.6 In a special embodiment, the "solvent" used is, for example, one that is customary for the plasticization of PVC, i.e. one that remains in the substrate and has to be removed by evaporation. There is no solvent.

The pigment preparations may be prepared in conventional manner by dispersing the compounds in conventional wet milling equipment, such as rotor-stator mills, bead mills, or ball mills. The particle size of the dispersed pigment should be between 0°2 and 2μ.

There are no restrictions on the pigments that are introduced into the pigment preparation according to the invention. It may be of organic or inorganic type. Examples of suitable organic pigments are pigments based on azo, anthraquinone, azoporphine, thioindigo, dioxazine, naphthalenetetracarboxylic acid or perylenetetracarboxylic acid, and lake-type dyes, such as dyes containing sulfonic and/or carboxylic acid groups. , Mg or AQ lake. Many of these are, for example, color indexes (Colour I
ndex) 2nd edition. Examples of suitable inorganic pigments are zinc sulphide, cadmium sulphide or cadmium selenide,
Ultramarine, titanium dioxide, iron oxide, nickel or chromium compounds as well as carbon black.

Suitable oligourethanes have a molecular weight of 5,000 to 50,000. Those with a molecular weight of 10,000 to 50,000 are preferred, and those with a molecular weight of 15,000 to 40,000 are particularly preferred. Very particular preference is given to oligourethanes which do not yellow or decompose due to oxygen, light, heat or water.

Currently available chain extending agents based on polyesters, polyethers, polycarbonates, polyether esters, isocyanates and glycols and/or amines can be used in the production of polyurethanes.

Adipic acid, succinic acid, geltaric acid, carbonic acid, phthalic acid, terephthalic acid, isophthalic acid, mono, di, tri and polyethylene glycol or mono, di, tri and polypropylene glycol, butanediol, hexanediol, polycaprolactone, these acids Polyesters obtained from mixtures of polyols and glycols with each other and with polyols containing amino groups are preferably used. Adipic acid, 7
Esters of tarric acid and carbonic acid are preferably used.

Polyneedle based on ethylene glycol, propylene glycol, butanediol (which can also be present as a mixture) which can be started with alcohols aminated or non-aminated by known methods can be used alone or in combination with ethers.

Essentially any polyisocyanate is suitable for the production of oligourethanes. Polyisocyanates such as polymerized or unpolymerized tolylene diphenyl diisonanate or methylene diphenyl diisocyanate or hexane diisocyanate or influorone diisocyanate are preferably used. Aliphatic isocyanates are particularly preferred because they are highly lightfast. The resulting oligourethanes can be present in OH-terminated, isocyanate-terminated or end-capped form.

The oligourethane preferably contains sterically hindered free or protected isocyanate groups.

The oligourethane used according to the invention is preferably N
Produced at a CO:OH ratio>1.

Suitable end-group protecting agents are primary, secondary or tertiary alcohols or oximes, such as butanone oxime.

Under the conditions using the pigment preparation, the protected isocyanate groups are liberated and can then react with, for example, the coating composition, coating or leather finish, thus improving its properties.

Organic leather finishing agents which can be colored with the pigment preparations according to the invention are disclosed, for example, in DE 1,174,937 and DE 1,278,064. Almost any binder that is soluble in organic solvents can be colored using the pigment preparations of the invention. They are particularly suitable for the coloring of aromatic and aliphatic polyurethane one-component systems as well as amine-containing two-component systems and for use in finishing surfaces based on cellulose derivatives, such as leather or leather substitutes.

The choice of pigment preparation is made depending on the desired color effect. If high hiding power is desired, preparations comprising inorganic pigments are used. On the other hand, if the treated substrate is expected to have a high gloss transparent color, preparations comprising organic pigments are used. Furthermore, attention is paid to the fastness properties associated with the pigments, such as light fastness, transport fastness, heat resistance, etc.

These new pigments can be used in reactive polyurethane systems, for example in the two-component process of DE 3.309.992, or in so-called high solids systems (DE 3.239.900).
Particularly suitable for use in applications (according to No. 1). Embodiments using oligourethanes with sterically hindered or protected isocyanates as composition components are particularly suitable for this application. Under application conditions, the composition components react with the reactive coating product.

The composition components are thus strongly incorporated into the coating.

In contrast to the known pigment preparations, the pigment preparation according to the invention is characterized by the fact that it is very easy to produce, is versatile, does not have an adverse effect on the finishes and substrates to be colored, and is especially suitable for pigments. It has the advantage of not impairing its robustness. -4
Oligourethanes with a softening point of 0 to +25°C are particularly suitable. After evaporation of any solvent that may be present in the drying oven, they do not form any continuous film from their solution in organic solvent. Surprisingly, they do not provide finish compositions that feel tacky or have poor heat abrasion resistance. The finish composition also has good low temperature resistance and good wet and dry bending strength.

Moreover, they do not migrate from the coating and finishing side threads. Adding plasticizers in the form of adipate or phthalate esters instead of solvents will prevent curing of either. 30% of these products based on the coating agent.
Hereinafter, when used in an amount of preferably 10% or less, these compounds do not migrate.

With pigment preparations comprising binders based on cellulose or polyvinyl acetate, it is often possible to improve the floating of organic pigments, especially in the case of mixtures of different pigments.
) occurs. This can be prevented using the pigment preparation according to the invention, and the compatibility with various coating agents is improved to an optimal extent, so that it is compatible with pigment binders, such as those used for printing textiles. Can be used for general purposes.

The following examples illustrate the present invention: 1. Example for the preparation of oligourethanes 1.2 Oligourethanes with protected isocyanate groups are described in this example: 63-70 (7) OH number (OH2000 1600 g of hexanediol neopentyl glycol adipate with 1 mmol) are completely dehydrated under reduced pressure and then in a 4Q stirred beaker 444 g of in7olone diisocyanate (N00400089 mol) and 80 g of triisocyanatohexylbiuret (NC020
0 mmol) until the theoretical NCO value is achieved (
That is, about 360 liters) was reacted at 90-100°C. The reaction mixture was then mixed with 240 g (2760 g) of butanone oxime.
mmol) and the reaction was allowed to proceed for an additional 200 minutes at 90-100°C with stirring. The concentration of the mixture was then adjusted to 70% with di-n-butyl phthalate. As a result, an oligourethane containing 2.80% of protected isocyanate groups and a viscosity of 2'2000 mPa5 at 25° C. was obtained.

Example 1.2 Hexanediol neopentyl glycol adipate 1 with an OH number of 63-70 (oH 2000 mmol)
600 g are completely dehydrated under reduced pressure and then in a 4Q stirred beaker 444 g of in7olone diisocyanate (N00400089 mol) and triisocyanatohexyl biuret 809 (NC0200
mmol) at 90-100°C until the theoretical NCO value was achieved (i.e. approximately 360 minutes). The reaction mixture was then further treated with 240 g (2760 mmol) of butanone oxime and the reaction was allowed to proceed for a further 200 minutes at 90-100° C. with stirring. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. This resulted in an oligourethane containing 2.80% of protected isocyanate groups with a viscosity of 230 Q mPa5 at 25°C. Example 1.3 Polypropylene glycol ether 20009 with an OH number of 56 (2000 mmol OH) is completely dehydrated under reduced pressure and then added to hexamethylene diisocyanate 354i+ (
NCO (420'O mmol) was reacted at 90-100°C until the theoretical NCO value was achieved (i.e. approximately 300 minutes). The reaction mixture was then diluted with butanone oxime 24
The reaction was further treated with 0 g (2760 mmol).
The mixture was allowed to proceed at 90-100°C with stirring for 00 minutes. The mixture was then brought to a concentration of 70% with methoxypropyl acetate.
Adjusted to %. As a result, 200mPa at 25℃
The protected isocyanate group has a viscosity of s 2.70
% was obtained.

Example 1.4 Hexanediol polycarbonate 20009 with an OH number of 56 (2000 mmol OH) was completely dehydrated under reduced pressure and then 444 g of in7olone diisocyanate (NGO40
00 mmol) and triisocyanatohexylbiuret 809 (NGO 200 mmol) and the theoretical Nc.

9 until a value of 2.67% is achieved (i.e. approximately 360 minutes)
The reaction was carried out at 0 to 100°C. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. A urethane having isocyanate groups and a viscosity of 1300 mPa5 at 25° C. was then obtained.

Example 1.5 Polypropylene glycol ether 20009 with an OH number of 56 (2000 mmol OH) is completely dehydrated under reduced pressure and then mixed with 2.4/2.6-diisocyanate in a stirred beaker at 4α. 1839 mmol of 1-methylbenzene (2100 mmol of NGO) and 176 g of hexamethylene diisocyanate (2100 mmol of NcO) were reacted at 90-100 DEG C. until the theoretical NCO value was achieved (ie about 200 minutes). The reaction mixture was then converted to butanone oxime 2409 (2760
(mmol) and the reaction was allowed to proceed for an additional 120 minutes at 90-100° C. with stirring. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate.

This resulted in an oligourethane containing 2.68% of protected isocyanate groups with a viscosity of 3 Q Q mPa5 at 25°C.

Example 1.6 Hexanediol neopentyl glycol adipate 1 with an OH number of 63-70 (2000 mmol OH)
600 g were completely dehydrated under reduced pressure and then 61 O g (4200 mmol NCO) of 1,3,5-triisopropylbenzene 2,4-diisocyanate (sterically hindered) in a 4Q stirred beaker, theoretical until an NCO value of 9 is achieved (i.e. approximately 300 minutes).
The reaction mixture was then further treated with 240 g (2760 mmol) of butanone oxime and the reaction was heated at 90-100"C with stirring for an additional 200 minutes.
Proceed at °C. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. As a result, 25°C
An oligourethane containing 2.60% of protected isocyanate groups with a viscosity of 3800 mPa5 was obtained.

2. Preparation of Pigment Preparation Example 2.1 1.8 kg of the pigment binder from Example 1.1 are diluted with 1.7 kg of di-n-butyl 7-talate to form a titanium dioxide pigment [
Bayer titan RFK-2
]6.5 kg were added and the mixture was stirred for 15 minutes at 200 Orpm using a solubilizer.

This was then ground in a ball mill to obtain a well-dispersed pigment paste.

Example 2.2 1.8 kg of the pigment binder from Example 1.2 are diluted with 85 g of methoxypropyl acetate and a mixture of trimethylbenzene (Zurpetz 1100 from ESSO) and added to the titanium dioxide pigment [Beyer Titanium RFDII 6.
5 kg and the mixture was mixed using a solubilizer for 1
Stir at 200 Orpm for 5 minutes. This was then ground in a bead mill to obtain a well-dispersed pigment paste.

Example 2.3 2.0 kg of pigment binder from Example 1.3 are diluted with 6.99 kg of methoxypropyl acetate and 109 kg of triethanolamine and then carbon black Mona, -
Monarch @ 800 [Cab
ot)] was added, and the mixture was stirred for 20 minutes at 2000 rpm using a solubilizer. The carbon black dispersion is then cooled and heated in a bead mill using 1 mm diameter glass beads until the required black depth and hiding power are achieved.
It was crushed twice.

Example 2.4 1.95 kg of pigment binder from Example 1.6 was combined with 1.3 kg of methoxypropyl acetate and Tsurpetz 100
(manufactured by ESSO), 5.5 kg of brown iron oxide pigment type 645T (manufactured by Bayer AG) were added and the mixture was stirred for 15 minutes at 2000 rpm+n using a solubilizer. This dark brown pigment dispersion is then applied in a 1.5 mm diameter until the required depth of color and hiding power is achieved.
It was ground once or twice before cooling in a bead mill using mm glass beads.

In order to produce pigment pastes of the same viscosity with other inorganic pigments, it is necessary to determine the pigment:binder ratio and solvent for each particular pigment.

Example 2.5 2.6 kg of pigment binder from Example 1.5 are diluted with 5.7 kg of methoxypropyl acetate and Novobalm (N
ovoperm ■) Red F5RK (manufactured by Hoechst) 1
．． 7 kg and the mixture was solubilized using a solubilizer.
Stirred at 000 rpm for 20 minutes. The pigment dispersion was then milled once or twice without cooling in a bead mill using 1 mm diameter glass beads until the required depth of color and gloss was achieved.

Example 2.6 2.2 kg of the pigment binder from Example 1.4 is diluted with 6.0 kg of methoxypropyl acetate to give 498 kg of Paliogen@ Red-Violet.
5 (manufactured by BASF) was added, and the mixture was stirred for 20 minutes at 2000 rpm using a solubilizer. The pigment dispersion was then ground one or two times without cooling in a bead mill using 1 mm diameter glass beads until the required depth of color and gloss was achieved.

Novobalm Red F5R5 and Variogen Red-
Similarly useful pigment preparations were made using other organic pigments in place of 4985 for violet. To obtain pigment pastes of the same viscosity, the pigment:binder ratio and solvent for each particular organic pigment should be adjusted as described for the inorganic pigments in Examples 2.1.2.2 and 2.4. It was necessary to decide.

Acetobutyrate varnish (see application example 3.1)
or collodion varnishes (see applications of Examples 3.2 and 3.3) or polyurethane solutions (Examples 3.4 to 3.1)
These pigment preparations can be used alone or in combination with the titanium dioxide pigment preparations described in Examples 2.1 and 2, 2, the carbon black pigment preparations (see Applications in Example 2.3). ), or in combination with the inorganic pigment preparation of Example 2.4.

All pigment pastes were well miscible with each other without flocculation and floating. Therefore, sedimentation, color streaks or discoloration are reverse coated.
It didn't happen in. The hues produced by this pigment preparation were well reproduced in all cases.

3. Coloring Example 3.1 Cellulose acetobutyrate butyryl content 49%, 2
Viscosity of 0% acetone solution at 20°C is approximately 20 Pas)
25g, di-n-butyl phthalate 5g, stearic acid n
- 4 g of butyl, 2 g of polyether siloxane (prepared according to Example 1 of DE 3,244,955)
, 1049 of 2-ethylhexyl acetate, 410 g of methoxypropanol and 410 g of n-butyl acetate, 40 g of the titanium dioxide preparation from Example 2.1.
g was added. After stirring for 5 minutes, a ready-to-use white paint was obtained which was easily sprayable and had excellent hiding power. It exhibited light fastness, amine fastness and yellowing resistance up to 170°C. This paint was particularly suitable as a high-hidden white finish on polished and perfectly textured leather.

Example 3.2 Ester-soluble collodion wool (wetted with butanol,
65%, standard form 9E) 329, 40 g of di-n-butyl phthalate, castor oil 159. Added with stirring. After stirring for 5 minutes, a strong black collodion paint was obtained which could be sprayed using a pneumatic spray gun. It was particularly suitable as a high gloss finish for polished and perfectly textured leather.

Example 3.2 Ester-soluble collodion wool (wetted with butanol,
65%, standard form 15E) 53g, di-n-butyl phthalate 24g, castor oil 4g, butyl stearate 8g, 2
The carbon from Example 2.3 is added to a solution consisting of 5 g of butyl I -ethylhexyl acetate, 2 g of triethanolamine, 159 g of di-n-octyl sodium sulfosuccinate, 12 g of the adduct of about 20 mol of ethylene oxide to 1 mol of nonylphenol. black preparation 50
9 was added with stirring. After the pigment dispersion was well dispersed, the mixture was emulsified with 525 g of water.

The resulting water-dilutable black emulsion was highly suitable as a strong black finish for thermoplastically finished, polished and perfectly textured leather.

Examples 3 and 4 Polyurethane resin (German Published Patent No. 2.4.23).

764), 130 g of tert-butanol, 100 g of toluene, trimethylbenzene [Solvesso' from ESSO
) l 0 0] 2 5 0 g, cellulose acetobutyrate (butyryl content 49%, 20° of 20% acetone solution)
Example 2 was added to a solution consisting of 3 g of polyethersiloxane (prepared according to example 2A of DE 3.244.955), methyl ethyl ketone 1009 and 260 g of methoxypropanol. 50 g of the iron oxide preparation from .4 were added with stirring. The final paint was sprayed with an airless spray gun and had a very good sheen with very good run-off and which is particularly suitable as a good hiding finish on furniture leather when applied to leather or leather imitations. It gave a soft brown finish.

Example 3.5 A pigmented polyurethane solution for coating textiles was prepared from the pigment preparation from Example 2.2 as follows; Titanium dioxide pigment preparation 89 from Example 2.2 was 25 g, 45 ao2 of dimethylformamide and 30 mQ of methyl ethyl ketone was added to a solution consisting of 25 ao2 of dimethylformamide and 30 mQ of methyl ethyl ketone while stirring at 200-300 rpm using a high speed stirrer. After stirring for 3-5 minutes, reverse the
A stable pigment dispersion was obtained which is highly suitable for coating textiles by the rsal process. In accordance with known techniques, the polyurethane film formed on the fabric with this method was uniform and free of spots. The component I polyurethane used was prepared from a polyester with an average molecular weight of 500 to 3000 obtained from adipic acid and hexanediol/neopentyl glycol and diphenylmethane 4,4'-diisocyanate, which was reacted together with butanediol.

Example 3.6 5 g of methyl ethyl ketone are added to a solution consisting of 30 g of crosslinkable polyurethane with terminal OH groups and 709 ethyl acetate, then Example 2.

8 g of titanium dioxide pigment preparation from 200 to 3
Addition was made under high speed stirring at 0.00 rpm. After stirring for 3 to 5 minutes, a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of toluylene diisocyanate and a heavy metal salt as promoter is added, suitable for coating textiles by the inverse method or by the direct method. A stable pigment dispersion was obtained. According to known methods,
The polyurethane formed by this method was uniform and free of spots.

Example 3.7 30 manufactured according to British Patent No. 1.418.550
% aliphatic polycarbonate-polyurethaneurea 100g
is the pigment li product 15 according to the invention from Example 2.5.
9 with mechanical agitation and the mixture was applied to embossed silicone release paper using a stationary doctor blade or similar known applicator. Coverage amount is 30g/m of solids! Met.

After passing through a drying oven heated to 80-125°C and then cooling, its hiding power was compared with that of other pigment preparations produced in a similar manner. The paste of ground pigment according to the invention had good hiding power.

Example 3.8 The topcoat described in Example 3.7 is unsuitable and therefore DM with a viscosity of 25000 mPa5/25 °C
Further aromatic polyurethane resin in F:MEK 50:50 had to be applied. Coverage amount is solid 5
The polyurethane resin was polypropylene glycol ether 2000 with a molecular weight of 2000.
g, ■, 200 g of 4-butanediol and 4.4'-
Prepared from 800 g of diphenylmethane diisocyanate.

To impart color, 20 g of the pigment preparation according to the invention from Example 2.5 were mixed in completely.

Example 3.9 Protected NGO prepolymer 10009 prepared according to Example 1 of DE 2.902.090,
Milled pigment paste loOg from Example 2.3, 3
, 3'-dimethyl-4,4'-diaminodicyclohexylmethane were mixed under reduced pressure while simultaneously heating to 40°C.

Coverage amount: 200g/m of solids! . Crosslinking temperature 150-160
The protected NCO prepolymer described above was used as an anchor coating by addition of diamine. 50 g of ground pigment paste from Example 2.3 and 200 g of 40% polyurethane resin dispersion
and 30 g of water-soluble silicone oil were thoroughly mixed with the dispersant.

This paste, which has a long shelf life at room temperature, was used directly on embossed release papers or on silicone matrices or on continuous steel strips.

All these temporary substrates could be coated with one or more coatings consisting of the products mentioned above or other chemicals (eg acrylates). The products were applied with known applicators (doctor blade, spray gun, roller, etc.).

Immediately thereafter, continuous materials such as woven, knitted, fleece and coagulated fabrics were layered and applied with a roller. This laminated material is passed through rollers made of various materials (metal, rubber, paper-based laminates, foam) and then heated for 13 minutes with heated circulating air.
Heat to 0-270°C and pass through a drying oven.

cooling the material on rollers at the exit from the dryer;
It was removed from a reusable separable carrier.

Example 3.10 The pigment preparations shown in Examples 2.1 to 2.6 were very suitable for coloring two-component polyurethanes which can be used for coating leather by the inversion process. The method was as follows: 200 g of p-tolylenediamine was dissolved in 800 g of methyl ethyl ketone over 5 minutes with stirring. 200 g of pigment preparation 2.4 were added to this tan solution.

Although this pigment preparation was dilute with water, it had a shelf life of several weeks and was very suitable for coating leather in the inversion process after reaction with polyisocyanates. Polyurethane films produced by this process according to known methods were uniform and spot-free. The polyisocyanate used was p'-toluylene diisocyanate,
It was produced by reacting with a polyester having a molecular weight of 1,000 to 3,000 produced from adipic acid, terephthalic acid and diethylene glycol.

Example 3. II Prepolymer A (see below) 342g (NGO262
(mmol) was treated with diamine coating solution 4259 (250 mmol) on the coating line using a two-component mix spray gun as described, for example, in U.S. Pat. No. 4,310,493. The composition of the hardener solution was as follows: 2800 parts of ethyl acetate 50s of iron oxide pigment treated according to Example 2.4 Ideal formula % Formula % where m is an integer from 27 to 35 and R is ethylene and 150 g split leather of propylene group J polyether polysiloxane,
Plain woven fabrics, fleeces and non-woven fabrics are described, for example, in US Pat.
310,493, by an inversion method using a spray gun for polyurethane resins. This spray gun machine includes a heated storage container for the shear polymer as the main component, a storage container for the curing agent preparation, a weighing device for the curing agent and for the prepolymer, and U.S. Pat. No. 4,310,493. a two-component polyurethane spray gun for mixing and atomizing the components as described in , a heatable inlet of the prepolymer;
It consisted of a curing agent inlet, a solvent inlet, and a compressed air inlet.

The prepolymer was placed in a heatable storage container and heated to 50-80°C to reduce its viscosity. The curing agent preparation was placed in a suitable container. The prepolymer and curing agent formulations were fed to the spray gun through separate conduits equipped with weighing devices. The feed rate was varied in the equivalent ratio of NCO:NH3 from 1°00=1 to 1.75:1. The coating rate was variable and depended on the desired film thickness and the area to be coated per unit time. The components of the reaction mixture are thoroughly mixed within the shortest possible time in the mixing space and mixing tube of a two-component polyurethane spray gun as detailed in U.S. Pat. No. 4,310,493, and Compressed air was expelled from the outlet nozzle. The reaction of the components took place at once, already during the mixing process.

At the outlet of the gun, the mixture is exposed to compressed air (working pressure 3-6
kg/cm”) is further mixed by the air vortex created by the
The triangular pyramid shape of the spray is transformed into a wide stream.

The gun is mounted on a matrix coated with silicone rubber (with the feel of natural rubber) or on another separate carrier.
It passed at a speed of about 25-30 @/min at 0 crn. Another carrier moved underneath the gun at a speed of 2-10 m/min. The material sprayed onto the matrix or separate carrier ran out into a film, the viscosity of the mixture increased and the material became pasty about 30-90 seconds after the start of the spraying operation. split leather or other materials,
Placed on or in the reaction material and pressed. The entire coating was then passed through a drying oven heated to 60-120°C. Approximately 3-6 minutes after the start of the spraying operation, the coating could be peeled off from the matrix or separable carrier without tack.

The polyurethaneurea film was 0.15-0.45 mm thick.

This coated flat material had a texture indistinguishable from natural leather, dried after a short time and could be ff-layered and processed, for example, by the modern shoe industry. The adhesion between the coating and the split leather was excellent, and the feel was pleasantly dry and soft.

Example 3.12 Prepolymer B (see below) 4749 (NC04
00 mmol) was treated with 130 g of the following hardener solution in a coating line in the same manner as Example 3.11: 2.4-1-Lylene diamine 400 g
Methyl ethyl ketone 6009
2.5 400 g of the above pigment suspension according to the invention
Flow control agent according to Example 3.11 1009
Surprisingly, it has been found that it is not necessary to keep this suspension of the various products suspended for long periods of time by mechanical stirring.

Under these conditions pigment dispersions usually tend to settle, but this did not occur in the case of the dispersions according to the invention. The pigment preparation according to the invention was further advantageous because no mechanical stirring was required and no air bubbles were introduced, ie air bubbles were not present in the cured film. Coatings on flat supports made from prepolymer and hardener solutions that are not mechanically stirred are
It is characterized by a dense film, that is, a film with increased strength because it contains less air.

Compared to the film obtained via a vessel equipped with a mechanical stirrer, the obtained film or coating had the following properties:

Container with stirrer Without stirrer Tensile strength 10 MPa 12)
JPa breaking elongation 440% 500% tear propagation resistance 22 daN 24 da
N Example 3.13 640 g (888 mmol) of Prepolymer 〇 (see below) were mixed well with 582 g of hardener preparation and poured onto a separable support.

This curing agent preparation corresponded to the following composition: Example 2.5
I PD using 120 g of pigment preparation from
Of the Al 709 (1 mol), a) 12.9 mol% is present as free IPDM, b) 41.6 mol% is present as, and c) 45.5 mol% is present as free IPDM. It exists as bis(methyl ethyl ketone) ketimine.

(The composition was calculated from the analysis of the mixture by gas chromatography.) In addition, the mixture contained a total of 37.9 g of water, calculated from the sum of the reaction water and a further 13 g of addition. (The amount of water theoretically required for the hydrolytic cleavage of the ketimine group to the amino group was 24.9 g.) The NH2 equivalent weight of the curing agent mixture was 6009.

Example 3.14 The carbon black preparation from Example 2.3 was highly suitable for coloring two-component polyurethanes for leather printing by the cold application method.

15 g of the carbon black preparation was added to a solution consisting of 709 crosslinkable polyester with a low degree of branching and terminal ○H groups, 30 g of ethyl acetate, 209 butyl acetate, 20 g of cyclohexanone and 109 methyl glycol acetate using a high-speed stirrer. Added with stirring under ~300 rpm+. After stirring for 5 minutes, a stable pigment dispersion was obtained. After adding 41 g of a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of lylene diisocyanate and heavy metals as promoters, it was suitable for printing leather by a cold coating process. According to known methods, the printed leather produced in this way was uniformly colored and free of spots. The black color was brilliant and had a high gloss. The polyester used was made from adipic acid, diethylene glycol and trimethylolpropane and had an average molecular weight of 1000-3000.

Example 3.15 The pigment preparation prepared according to Example 1 of German Patent Application No. 2.801,817, pages 7-8, line 3, was most suitable for application alone. However, it has been shown that mixtures of organic pigments with inorganic pigments, all made using the same pigment binder, do not remain homogeneously mixed without constant mechanical stirring. Particularly after the prepared solution was allowed to stand for a long period of time, sedimentation of particularly heavy inorganic pigments and floating of particularly light organic pigments could be observed.

Examples 3, 16 The final preparations comprising the collodion pigment preparations were only suitable to a limited extent for use on soft materials, such as those represented by leather, woven fabrics, fabrics, and the like.

Pigment preparations using collodion as a composition agent with or without the addition of plasticizers have shown an adverse effect on the properties of soft finishes such as those based on polyurethane, such as leather and leather imitations. After long-term storage, it hardens the leather or leather imitation, impairs feel and texture, reduces bending strength, and impairs low temperature resistance. Lightfastness and yellowing under the influence of heat and amines as well as adhesion are particularly adversely affected by these pigment preparations.

4. Preparation of NCO prepolymers for Examples 3.11 to 3.13 Prepolymer A 60 parts of hydroxyl number 64 (OH73.5 equivalents) obtained from adipic acid, hexanediol and neopentyl glycol were added to llo'c. Water was removed in a pressure solution for 1 hour and 12.8 toluylene diisocyanate (80% 2,4-isomer and 2.6 = 20% isomer, 147 equivalents) in the presence of 18.2 parts of toluene part and 1
．． The reaction was carried out at 10°C to produce a prepolymer with an NGO content of 3.2%. This viscosity is 4000 mP at 20°C
a5 and 500 mPa5 at 70°C.

Prepolymer B Water was removed from 500 g of polyester prepared from adipic acid and ethylene glycol (0.53 mol) at 13 torr and 110° C. for 1 hour. This polyester was then heated at 110°C for 6 hours with 132 4'-diisocyanatodiphenylmethane (NC01.06 mol).
．． It was reacted with 5g.

A prepolymer with an NGO content of 3.54% was obtained.

Prepolymer C 50% by weight of ethylene oxide and 5% of propylene oxide
From 0% by weight (starting with l, 2-propylene glycol)
O obtained (starting with glycerol) from 100 g of the obtained linear polyether with a hydroxyl number of 56 and 27.5% by weight of propylene oxide and 72.5% by weight of ethylene oxide.
HHSO33 functional polyether 10009 was dehydrated and reacted with 666 g of 4,4'-diphenylmethane diisocyanate at 90°C. Reaction time was 45 minutes, N
The GO content was 5.8% and the equivalent weight was 724.

Claims (1)

Claims: 1. Comprising: 1. A) an inorganic and/or organic pigment, B) a liquid oligourethane, and, if appropriate, C) one or more additives customary for pigment preparations. , but A):B)
A pigment preparation having a weight ratio of 1:0.1 to 50. 2. A) 2-60% by weight of an organic pigment, B) 5-98% by weight of an oligourethane, and C) an additive, in particular a solvent, 5-90% by weight, provided that A) + B) + C) in total 10
Pigment preparation according to claim 1, which contains 0% by weight. 3. A) 5-30% by weight of organic pigments, B) 5-98% by weight of oligourethanes, and C) additives, especially 8-90% by weight of solvents, provided that A) + B) + C) in total. 10
Pigment preparation according to claim 1, which contains 0% by weight. 4. A) 2-80% by weight of an inorganic pigment, B) 5-98% by weight of an oligourethane, and C) an additive, in particular a solvent, 5-90% by weight, provided that A) + B) + C) in total 10
Pigment preparation according to claim 1, which contains 0% by weight. 5. A) 10-65% by weight of inorganic pigments, B) 5-98% by weight of oligourethanes, and C) additives, especially solvents 8-90%.
% by weight, provided that A) + B) + C) totals 1
2. Pigment preparation according to claim 1, which contains 0.00% by weight. 6. The pigment preparation according to any one of claims 1 to 5, wherein the oligourethane has a molecular weight of 5,000 to 50,000. 7. The molecular weight of oligourethane is 15,000 to 40,000
A pigment preparation according to any one of claims 1 to 5. 8. The pigment preparation according to any one of claims 1 to 7, wherein the oligourethane has a sterically hindered isocyanate group. 9. The pigment preparation according to any one of claims 1 to 8, wherein the oligourethane has a protected isocyanate group. 10. Use of the pigment preparation according to any one of claims 1 to 9 for coloring leather and finishing agents for leather cloth.